CN104011120A - High-temperature peroxide-containing styrene polymer beads for seed polymerization - Google Patents
High-temperature peroxide-containing styrene polymer beads for seed polymerization Download PDFInfo
- Publication number
- CN104011120A CN104011120A CN201280063951.2A CN201280063951A CN104011120A CN 104011120 A CN104011120 A CN 104011120A CN 201280063951 A CN201280063951 A CN 201280063951A CN 104011120 A CN104011120 A CN 104011120A
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- China
- Prior art keywords
- weight
- styrene polymer
- polymer bead
- styrene
- bead
- Prior art date
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- Pending
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 219
- 239000011324 bead Substances 0.000 title claims abstract description 134
- 229920000642 polymer Polymers 0.000 title claims abstract description 121
- 150000002978 peroxides Chemical class 0.000 title abstract description 7
- 238000006116 polymerization reaction Methods 0.000 title description 23
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
- 239000000725 suspension Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 34
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 29
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 229910002804 graphite Inorganic materials 0.000 claims description 27
- 239000010439 graphite Substances 0.000 claims description 27
- 239000008187 granular material Substances 0.000 claims description 22
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 21
- 239000000654 additive Substances 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 239000003063 flame retardant Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 230000009466 transformation Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000000203 mixture Substances 0.000 description 29
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 description 22
- 229920006248 expandable polystyrene Polymers 0.000 description 22
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 20
- 238000009826 distribution Methods 0.000 description 19
- 239000000178 monomer Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- 239000004793 Polystyrene Substances 0.000 description 14
- 239000003995 emulsifying agent Substances 0.000 description 14
- 229920002223 polystyrene Polymers 0.000 description 14
- -1 titanium dioxide Chemical class 0.000 description 14
- 239000012074 organic phase Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 238000012216 screening Methods 0.000 description 13
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 11
- 239000004606 Fillers/Extenders Substances 0.000 description 10
- 235000019341 magnesium sulphate Nutrition 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 7
- 239000008199 coating composition Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229940075507 glyceryl monostearate Drugs 0.000 description 6
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 150000003440 styrenes Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 238000005502 peroxidation Methods 0.000 description 5
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- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000002352 surface water Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- VISLHMUTPUAARK-UHFFFAOYSA-N butyl 2-ethylperoxyhexanoate Chemical compound CCCCOC(=O)C(CCCC)OOCC VISLHMUTPUAARK-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical class 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 235000019241 carbon black Nutrition 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 159000000003 magnesium salts Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- HORIEOQXBKUKGQ-UHFFFAOYSA-N bis(7-methyloctyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCC(C)C HORIEOQXBKUKGQ-UHFFFAOYSA-N 0.000 description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 229940078499 tricalcium phosphate Drugs 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- KKFBZUNYJMVNFV-UHFFFAOYSA-N 1,2-bis(2-methylpropyl)naphthalene Chemical compound C1=CC=CC2=C(CC(C)C)C(CC(C)C)=CC=C21 KKFBZUNYJMVNFV-UHFFFAOYSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical group CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- GMCOJPKLRGEOOM-UHFFFAOYSA-N C(CCCCCCCCCCC)[SiH](C)C.[Cl] Chemical compound C(CCCCCCCCCCC)[SiH](C)C.[Cl] GMCOJPKLRGEOOM-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 101000648997 Homo sapiens Tripartite motif-containing protein 44 Proteins 0.000 description 1
- 241001397173 Kali <angiosperm> Species 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 239000003963 antioxidant agent Substances 0.000 description 1
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- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical group [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
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- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
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- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
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- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
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- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
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- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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Abstract
The invention relates to styrene polymer beads, characterized in that the styrene polymer beads contain 0.5 to 5 wt% of one or more high-temperature peroxides, wherein the high-temperature peroxides have a half-value period of one hour in the range of 110 to 160 DEG C, measured in cumene.
Description
The present invention relates to styrene polymer bead, it has the particle diameter within the scope of 0.2 to 1.5mm, one or more high temperature superoxide that wherein styrene polymer bead comprises 0.5 to 5 % by weight, and relate to the method for preparing this styrene polymer bead, and relate to this styrene polymer bead as the purposes of the seed in suspension polymerization.
Suspension polymerization is widely used in preparing Expandable Polystyrene (EPS) (EPS).Suspension can be for example by stablizing as the magnesium pyrophosphate in EP-A575872 as polyvinylpyrrolidone or so-called Pickering stablizer with protective colloid.Bead size and bead size-grade distribution can be controlled by the amount of stablizer and the addition manner of stablizer.
Add the graphite as infrared absorbent to obtain following expandable styrene-polymer, this expandable styrene-polymer can obtain having under low density through processing the lagging material (US6,130,265) of the thermal insulation of improvement.Herein, thermal conductivity is significantly reduced by reducing ultrared amount.Similarly improvement can realize as carbon black, silicate and aluminium with other IR absorption agents.
As normally problematic in polymerization under the existence of granular IR absorption agent or fire retardant at surfactant additive because described additive can make suspension unstable and can cause cohesion.Therefore; WO 99/16817 and WO 03/033579 have proposed; for the suspension polymerization under the existence of graphite granule, use for example t butyl 2 ethyl peroxyhexanoate (it can not form any benzoyl group or benzyl group) and use the different superoxide with different decomposition temperature of specific peroxide initiator.
By suspension polymerization, the EPS bead that particularly obtains under the existence of graphite, the larger variation that conventionally shows the median size between wide size-grade distribution and various production batch.This just requires follow-up screening, to obtain, has the product that adapts to particle diameter.Required sieve fraction is conventionally in 0.8 to 2.0mm scope.
WO 00/61648 has described a kind of multistage seeding polymerization method of preparing the polymer beads with at least 50 μ m median sizes, and the method is carried out as follows: by means of diffusion, initiator is inserted to seed, and therefore make seed activation.
For example, JP-A2009-138146 discloses under the existence of the seed of making at polystyrene, is prepared the method for expandable styrene-polymer particle by vinylbenzene, alpha-methyl styrene and Vinylstyrene by suspension polymerization.Conventionally use peroxide initiator as polymerization starter herein, it is not only for the preparation of seed, and for follow-up suspension polymerization.
The method of preparing the Expandable Polystyrene (EPS) that comprises carbon black or comprise graphite by seeding polymerization is known in for example WO 2010/06631, US 2009/0030096A1 or JP-A62-13442.To be used as the seed in follow-up suspension polymerization by mixing graphite to be introduced into polystyrene melts and extruding the particulate (minipellet) obtaining with granulation herein.Yet the particle diameter of seed is limited to the minimum diameter of granulation mould (pelletizing die).In addition, thermo-sensitivity additive, for example fire retardant is as HBCD, or superoxide is as dicumyl peroxide, in the situation that not decomposing at least partly, can not be introduced into seed.In addition, it is debatable extruding the bead with high content of graphite, and reason is, the high melt viscosity of this bead and the obstruction of granulation mould.
An object of the present invention is to provide the styrene polymer bead that comprises one or more high temperature superoxide, so as this styrene polymer bead can be used as suspension polymerization seed and without further adding superoxide.Especially, styrene polymer bead should not contain volatile foaming agent, but should comprise conventional auxiliary agent, particularly particulate additives.
The styrene polymer bead material of claim 1 has realized this object.
Preferred embodiment is found in dependent claims.
Styrene polymer bead of the present invention comprises 0.5 to 5 % by weight, preferred one or more high temperature superoxide of 1 to 4 % by weight.
Preferably, styrene polymer bead comprises 0.5 to 5 % by weight, particularly preferably 1 to 4 % by weight is as the dicumyl peroxide of high temperature superoxide.
Styrene polymer bead has 0.2 conventionally to 1.5mm, preferably the bead size within the scope of 0.3 to 1.3mm.Bead size can be measured by screen analysis, wherein at least 94% sieve fraction have 0.2 to 1.5mm, preferred 0.3 to 1.3mm bead size.
Preferably, except high temperature superoxide, styrene polymer bead also comprises one or more particulate additives of 5 to 50 % by weight, the particularly carbon granule of 5 to 50 % by weight.Particularly preferably, the graphite granule of the median size that styrene polymer bead comprises 5 to 50 % by weight within the scope of 1 to 50 μ m.
The graphite granule of the median size that particularly preferred styrene polymer bead comprises 5 to 30 % by weight within the scope of 1 to 50 μ m and 5 to 30 % by weight are as brominated styrenic polymer or the brominated styrene butadiene block copolymer of fire retardant.
Preferably, styrene polymer bead is not containing whipping agent.This makes to transport facility and safety.The styrene polymer bead containing whipping agent does not at room temperature have the preservation period of several months.
Styrene polymer bead of the present invention can for example be prepared by the method comprising the following steps:
A), under the existence of high temperature superoxide, the first suspension polymerization of the waterborne suspension by comprising styrene monomer and optional particulate additives is prepared styrene polymer bead,
B) separating phenylethylene polymer beads, and
C) optionally sieve from styrene polymer bead, to extract one or more sieve fractions.
In the method for a preferred preparation styrene polymer bead of the present invention, polymerizing styrene monomer in waterborne suspension under the maximum temperature of 130 ℃ under the existence of the high temperature superoxide of 0.5 to 5 % by weight and the low temperature superoxide of 0.1 to 3 % by weight, wherein said suspension polymerization is less than the time of 1.5h under the temperature range of 120-130 ℃.
Styrene polymer bead of the present invention is particularly suitable as the seed in suspension polymerization.
Therefore, the present invention also provides a kind of method of preparing expandable styrene-polymer, wherein uses styrene polymer bead of the present invention as the seed in styrene monomer suspension polymerization, and during polyreaction or add afterwards whipping agent.The second suspension polymerization---hereinafter referred to as steps d)---can carry out, for example, after styrene polymer bead is delivered to another production, carry out in independent process:
D) prepare the waterborne suspension of styrene polymer bead, and under the existence of whipping agent and add under the condition of styrene monomer and carry out the second suspension polymerization.
Statement " expandable styrene-polymer " refers to the styrene polymer bead that contains whipping agent.
Operable styrene polymer is homopolymer or the multipolymer of being made by vinylbenzene, styrene derivatives or copolymerizable ethylenically unsaturated monomers.These homopolymer or multipolymer step a) and d) in suspension polymerization by vinylbenzene and suitable copolymerizable monomer form, described suitable copolymerizable monomer is for example, ring-alkylated styrenes, Vinylstyrene, Isosorbide-5-Nitrae-tetramethylene dimethacrylate, p-methyl-alpha-methyl styrene, alpha-methyl styrene or vinyl cyanide, divinyl, acrylate or methacrylic ester.Particularly preferably, in all polymerization procedures, only use vinylbenzene as monomer.
Cinnamic suspension polymerization itself is known.It is recorded in Kunststoff-Handbuch in detail, Band V, " polystyrene " [plastics handbook, V volume, " polystyrene "], Carl Hanser-Verlag, 1969, the 679 to 688 pages.Herein, conventional steps is to make vinylbenzene suspends in water, then under the existence of organic or inorganic suspension stabilizer, completes the polymerization of described material---optionally together with above-mentioned comonomer---.The volume ratio of water and organic phase is preferably 0.5 to 1.6, and particularly 1.0 to 1.4.
Step a)
Operable particulate additives is for being substantially not dissolved in any additive of styrene polymer.The material that is preferably used as particulate additives is IR absorption agent, for example metal oxides such as titanium dioxide, or carbon granule.Operable carbon granule is various natural or synthetic carbon blacks or graphite.Preferably, carbon granule comprises that ratio is the graphite-structure of at least 1 % by weight, preferred at least 5 % by weight.The ash oontent of the carbon granule of measuring according to DIN51903 is preferably 0.005 to 15 % by weight, preferably 0.01 to 10 % by weight.Particularly preferably use the graphite granule of median size within the scope of 1 to 50 μ m as particulate additives.
The median size of the graphite preferably using is preferably 1 to 50 μ m, particularly 2.5 to 12 μ m, and its bulk density is preferably 100 to 500g/l, and its specific surface area is preferably 5 to 20m
2/ g.The synthetic graphite that can use natural graphite or grind.
The overall proportion of all particulate additives is preferably 5 to 40 % by weight, particularly 10 to 30 % by weight, styrene-based polymer beads meter.Particularly preferably only use carbon granule, particularly graphite as particulate additives.
The graphite granule of the median size of using styrene-based polymer beads meter 10 to 30 % by weight particularly preferably in step in a) within the scope of 1 to 50 μ m is as particulate additives.
Can also use silane-modified carbon granule as carbon granule, described silane-modified carbon granule by 0.01 to 1 % by weight for example, preferably 0.1 to 0.5 % by weight is silane-modified, based on carbon granule meter.
Silane-modified carbon granule preferably has C in its surface
3-C
16-alkyl silane group or aryl-silane group, particularly C
6-C
12-alkyl silane group or phenyl silane group.Specially suitable material for carbon modified particle is alkyl silane or the aryl-silane on Siliciumatom with 1 to 3 halogen atom or methoxy group.Preferably use C
3-C
16-alkyl silane or aryl-silane, particularly octyl group trichlorosilane, chlorine (dodecyl) dimethylsilane, hexadecyl Trimethoxy silane or phenyl-trichloro-silicane.
With silane-modified, cause carbon granule surface by silyl and hydrophobization, thereby significantly reduced the interfacial activity of carbon granule, described interfacial activity can be destroyed suspension process.Unexpectedly, itself known for the method that for example, makes water-wetted surface hydrophobization by silanization at gas phase or solvent (toluene) also in the situation that relatively hydrophobic graphite work, to shelter remaining polar group.The surface modification of carbon granule can obtain better and the consistency of polymeric matrix, or even is bonded in polymeric matrix.
Except particulate additives, can be added to the material of step in a) and also can be conventional substance, for example fire retardant, nucleator, UV stablizer, chain-transfer agent, softening agent, pigment and antioxidant.
Except listed above additive, the material that can be used for suspension polymerization also can be in particular conventional peroxide initiator and suspension stabilizer, for example protective colloid, inorganic Pickering salt and negatively charged ion and nonionogenic tenside.
Substance used is preferably halogen containing flame-retardant or halogen-free flame retardants.Specially suitable is organbromine compound, aliphatic, alicyclic and aromatic bromine compound particularly, example is hexabromocyclododecane (HBCD), pentabromo-monochloro hexanaphthene, penta-bromophenyl allyl ethers, or brominated styrenic polymer, styrene-butadiene block copolymer for example, wherein these materials can be used separately or use with the form of its mixture.Preferably, fire retardant used only comprises brominated styrenic polymer or brominated styrene-butadiene block copolymer.
As the molecular-weight average of the halogenated polymer of fire retardant, preferably 5000 to 300 000, particularly in 30 000 to 150 000 scope, by gel permeation chromatography (GPC), in tetrahydrofuran (THF), using polystyrene and measure as standard substance.
At 250 ℃ or higher, preferably, at 270 to 370 ℃ of temperature, the weight loss of halogenated polymer in thermogravimetric analysis (TGA) is 5 % by weight.
The effect of brominated flame-retardant can be by adding the unsettled organic compound of C-C-or O-O-to improve.The example of suitable retardant synergist is diisopropylbenzene(DIPB) and dicumyl peroxide.Preferred combination is comprised of the organbromine compound of 0.6 to 5 % by weight and the C-C-of 0.1 to 1.0 % by weight or the unsettled organic compound of O-O-.
Conventionally in step, use in a) 0.1 to 10% white oil or Hexamoll Dinch as softening agent, to improve the foaminess of final product.
Can use the phosphoric acid salt based on water meter 0.3 to 5 % by weight, preferred magnesium pyrophosphate or tricalcium phosphate to carry out stabilized aqueous suspension.Particularly preferably use magnesium pyrophosphate.
Particularly when using a high proportion of particulate additives, except magnesium pyrophosphate, in step, also add bitter salt in a), with stabilized aqueous suspension.Preferably add the bitter salt based on water meter 0.05 to 1 % by weight.Also particularly preferably add the bitter salt based on organic phase meter 0.1 to 0.5 % by weight.Organic phase is comprised of monomer and optional styrene polymer and water-fast additive.
Magnesium pyrophosphate preferably before polyreaction immediately by making the pyrophosphate solution of peak concentration and magnesium ion solution in conjunction with preparing, wherein the consumption of magnesium salts is precipitation Mg
2p
2o
7required stoichiometry.Magnesium salts can solid form or the existence of aqueous solution form.In a preferred embodiment, magnesium pyrophosphate is by making trisodium phosphate (Na
4p
2o
7) aqueous solution and magnesium sulfate (MgSO
47H
2o) aqueous solution in conjunction with and prepare.The add-on of magnesium salts is at least required stoichiometry, and is preferably stoichiometry.For method of the present invention, advantageously avoid the existence of any excessive alkali metal pyrophosphate.
In the method for the invention, preferably use the emulsifying agent that contains sulfonate group, be also called extender (extender).Described extender is for example Sodium dodecylbenzene sulfonate, chain alkyl sulfonate, vinylsulfonate and diisobutyl naphthalene.An alkali metal salt and/or C that the extender preferably using is Witco 1298 Soft Acid
12-C
17an alkali metal salt of the mixture of-alkylsulphonic acid.Specially suitable C
12-C
17the mixture of-alkylsulfonate is mainly C by mean chain length
15alkylsulphonic acid disodium hydrogen (secondary sodium alkylsulfonate) form.This class mixture is sold as E30 business by Leuna Tenside GmbH.Under the existence of slightly soluble mineral compound, extender more easily makes effect suspension stabilization.
Extender consumption is generally 0.5 to 15 % by weight, preferred 2 to 10 % by weight, based on magnesium pyrophosphate meter.
In order to improve the stability of the suspension in polymerization process, particularly, before adding extender, need to improve agitator speed according to the character of agitator used and reactor.Preferably Mean Input Power is greater than the every 1kg reactor content of 0.2W/.
If the median size of styrene polymer bead is too small, can reduces the amount of extender used, or can after adding extender, reduce agitator speed, so that the set(ting)value of Mean Input Power is lower than 0.2W/kg.
Have been found that a favorable factor for stability of suspension is, when suspension polymerization starts, have polystyrene (or suitable styrol copolymer) solution of (or in mixture of vinylbenzene and comonomer) in vinylbenzene.The preferred polystyrene with concentration 0.5 to 30 % by weight, particularly 3 to 20 % by weight is in the solution in vinylbenzene herein.Pure polystyrene can be dissolved in monomer herein, but advantageously use so-called border fraction (marginal fraction), described border fraction is the excessive or too small bead removing in the size classification process of the bead that produces in preparing Expandable Polystyrene (EPS) process.Particularly preferably use at step c herein) in the step that shifts out border fraction a).
Preferably, except conventional superoxide, in step, also use at least one high temperature superoxide in a).Statement " high temperature superoxide " refers within the scope of 110 to 160 ℃, preferably within the scope of 120 to 140 ℃, particularly preferably within the scope of 125 to 135 ℃ in isopropyl benzene the transformation period be the superoxide of 1 hour.The example of suitable superoxide is two t-amyl peroxy things, peroxidized t-butyl perbenzoate, two (tert-butyl hydroperoxide sec.-propyl) benzene, 2,5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) hexane and dicumyl peroxide.Particularly preferably use dicumyl peroxide as high temperature superoxide.
Step a) in, the total amount of at least one the high temperature superoxide using is generally at least 0.5 % by weight, preferably within the scope of 1.1 to 5.0 % by weight, within the scope of 1.3 to 4 % by weight, styrene-based polymer beads meter.
Rapid a) in, particularly preferably use the graphite of 5 to 50 % by weight and the dicumyl peroxide of 0.5 to 5 % by weight, styrene-based polymer beads meter separately, and at the temperature of 120 to 130 ℃, carry out the time that suspension polymerization is less than 1.5 hours particularly preferably in step in a).The prepolymer of the undecomposed dicumyl peroxide that the method obtains comprising q.s, and the method makes in steps d) in without adding other superoxide to carry out suspension polymerization.In addition, this material also can be used as the retardant synergist in expandable styrene-polymer.Preferably, in styrene polymer bead, the amount of undecomposed remaining high temperature superoxide is 50 to 100 % by weight, 60 to 80% weight particularly, the amount meter based on used.Described remaining high temperature superoxide can be used as unique polymerization starter in main polyreaction (steps d).
Therefore, the present invention also provide comprise 5 to 50%, the preferably graphite of 10 to 30 % by weight and 0.5 to 5 % by weight, preferably the styrene polymer bead of the dicumyl peroxide of 1 to 4 % by weight, separately styrene-based polymer beads meter.
Step b)
First the styrene polymer bead of gained is separated from water.Described styrene polymer bead can be directly used in main polyreaction (steps d) subsequently, or is divided into each fraction and selects particle size fraction (step c), is used further to main polyreaction (steps d).
Step c)
At optional step c) in, styrene polymer bead is divided into different particle size fractions, and selects one or more fractions for subsequent step.Stage division generally includes the screening-extraction (sieve-extraction) of one or more sieve fractions.The size of expandable styrene-polymer bead targetedly mode is controlled by sieving styrene polymer bead in suitable optional mode.Preferably, at step c) in, by screening extract bead size 0.2 to 1.5mm, the preferred sieve fraction of the styrene polymer bead within the scope of 0.3 to 1.3mm.
Steps d)
In steps d) in carry out the second suspension polymerization at least one times.This means that this step can carry out with two steps or multistep.For example,, step b) to d) can carry out repeatedly, wherein at least one times suspension polymerization under the existence of whipping agent and add under the condition of styrene monomer and carry out.Yet, preferably, method of the present invention by implementation step a), b), c) and d) once and carry out with two stages.
In at least the second suspension polymerization, at step b) in separated polymer beads or step c) in one or more prepolymer bead fractions of selecting as the initial charge of waterborne suspension.
Suspension polymerization compared to step in a), wherein all the styrene monomers of amount are typically used as initial charge, steps d) in the preferred continuous measurement of styrene monomer be added in mixture.Herein, based on expandable styrene-polymer meter, 10 to 60 % by weight, preferably 15 to 35 % by weight, particularly preferably 25 to 35 % by weight styrene monomer conventionally with the form initial charge of styrene polymer bead to water, and remainder is with monomer, particularly preferably the form continuous measurement with styrene monomer is added to mixture.Before polyreaction starts, styrene polymer bead can be first carries out initial swelling with organo-peroxide as t butyl 2 ethyl peroxyhexanoate at the temperature lower than polymerization temperature.In addition, verified, it is also favourable at the temperature lower than polymerization temperature, adding white oil or adding a part for styrene monomer to be added.
Steps d) optionally use particulate additives and the substance of step described in a).
In order to stablize the second suspension polymerization, also use phosphoric acid salt, preferably magnesium pyrophosphate or tricalcium phosphate.The initial charge that magnesium pyrophosphate is typically used as polyreaction while starting, and in steps d) in, the concentration of magnesium pyrophosphate is generally 0.03 to 2.0 % by weight, is preferably 0.05 to 0.5 % by weight, is particularly preferably 0.1 to 0.2 % by weight, based on water meter.
In addition, extender is equally as steps d) in the initial charge of polyreaction before starting, be added in water.The consumption of weighting agent is generally 0.5 to 15 % by weight, is preferably 2 to 10 % by weight, based on magnesium pyrophosphate meter.
Whipping agent used be generally have 3 to 10, the preferred aliphatic hydrocrbon of 4 to 6 carbon atoms, for example, Skellysolve A, iso-pentane or its mixture.The add-on of whipping agent is generally 1 to 10 % by weight, preferred 3 to 8 % by weight, the weighing scale of the styrene polymer based on existing in expandable styrene-polymer.
Styrene polymer bead used shared ratio in water is generally 10 to 60 % by weight, is preferably 20 to 40 % by weight, based on expandable styrene-polymer meter.
In steps d) in, adding conventionally of styrene monomer carried out continuously, carries out in preferably during 1 to 5 hour., at one, be proved to be in favourable method herein, before the heating phase finishes, at the temperature lower than 100 ℃, the styrene monomer to be added of 5 to 15 % by weight be added in reactor.
In steps d) in, polyreaction is preferably carried out at least to a certain degree at the temperature of 115 to 130 ℃.
Preferably in steps d) in do not add peroxide initiator.Especially, when styrene polymer bead comprises high-temperature initiator as dicumyl peroxide as described above, can save and use conventional low temperature initiators as t butyl 2 ethyl peroxyhexanoate.This tool has the following advantages: the polyreaction steps d) can be carried out at the temperature higher than 120 ℃, and result can reduce polymerization time.In addition,, because vinylbenzene at the temperature higher than 120 ℃ is faster to the diffusion at bead center, therefore between the easier core at bead polymers and outer peripheral areas, realize uniform Graphite Distribution.It is problematic when main polyreaction starts, adding subsequently dicumyl peroxide, because dicumyl peroxide is only not exclusively absorbed by styrene polymer bead, and decompose to a certain extent under conventional polymerizing condition, obtain hydrogen phosphide cumene, this causes carrying out parallel letex polymerization in water.Consequently form very a large amount of white and the secondary polymkeric substance of graphitiferous not.
The expandable styrene-polymer bead obtaining by the inventive method can apply with conventional coating composition, and described coating composition is metallic stearate, glyceryl ester and fine grain silicon hydrochlorate for example.
Steps d) in preparation the styrene polymer beads that comprises whipping agent typically have a diameter from 0.2 to 4mm, preferably 0.7 to 2.5mm.This styrene polymer beads can for example carry out pre-frothing with steam by means of ordinary method, obtain diameter and be 0.1 to 2cm and bulk density be 5 to 100kg/m
3foam beads.
The particle of pre-frothing can foam to completely by ordinary method subsequently, obtains density and be 5 to 100kg/m
3foam molded articles.
Can process the expandable styrene-polymer obtaining by the method, take and obtain density as 5 to 35g/l, preferably 8 to 25g/l and 10 to 15g/l polystyrene foam particularly.For this reason, expandable particles is by pre-frothing.This mainly by realizing with steam heating particle in so-called pre-foaming machine (prefoamer).
Then make the particle of pre-frothing thus carry out melting to obtain moulded product.For this reason, the particulate charge of pre-frothing is not extremely carried out in the mould of gas-tight seal, and process with steam.After cooling, shift out moulded product.
The foam characteristics being made by expandable styrene-polymer is the heat insulation of excellence.Described effect is remarkable especially under low density.The reduction of thermal conductivity is enough large, makes material meet the requirement (according to DIN18164, part 1, table 4) of thermal conductivity classification 035.
The embodiment of the suspension polymerization of the method is characterised in that and is showing the stability that has increased suspension, and there is no inversion of phases.The stability of the suspension improving provides a reliable and more effective method.By means of the stablizer of small amount, realized bead size-grade distribution has been controlled better.Significantly reduced the interior moisture content of the expandable styrene-polymer obtaining.
The method can increase and has productive rate, the particularly productive rate in the expandable styrene-polymer of graphitiferous required and fraction vendible bead size-grade distribution.If save the screening to styrene polymer bead material, the conventional suspension polymerization under existing with at graphite is compared, and still can realize narrower size-grade distribution, that is, and and the productive rate of higher useful fraction.
Embodiment
Except as otherwise noted, as follows for the raw material of embodiment:
Bead size-grade distribution is measured by screen analysis (standard 1), and with granularity GS and relative content (R) assessment.
β value is defined as follows, and distributes based on Rosin distribution, Rammler distribution, Sterling distribution, Bennet; * 180 °/π of β=arctan (1/n); N=ln (ln (1/R))=n*ln (d wherein
sieve hole)-n*ln (d`); R=exp ((d
sieve aperture/ d`)
n); d
sieve aperture: the sieve aperture width of each sieve, d ': accumulate Rosin size-grade distribution, accumulation Rammler size-grade distribution, accumulation Sterling size-grade distribution, accumulate Bennet size-grade distribution in the median size at 63 % by weight places.
Mg
2p
2o
7the preparation of suspension:
Following examples are used freshly prepared amorphous magnesium pyrophosphate precipitation (MPP suspension) as Pickering stablizer.In each following embodiment, Mg
2p
2o
7suspension is prepared as follows in advance: at room temperature (25 ℃) are by 931.8g trisodium phosphate (Na
4p
2o
7, purchased from Giulini) be dissolved in 32kg water; By 1728g bitter salt (Epsom salt, MgSO
4x7H
2o) add to the solution stirring in 7.5kg softening water in above-mentioned solution, then this mixture is stirred 5 minutes.Obtain the waterborne suspension of magnesium pyrophosphate (MPP).
Comparative example 1 (with US6,130,265 embodiment 1 is similar)
Prepare by the following method organic phase: by 2.30kg PS158K polystyrene, 54g dicumyl peroxide (Perkadox BC-FF, purchased from AkzoNobel) and the dibenzoyl peroxide (Lucidol75 of 24.5g75% concentration, AkzoNobel) be dissolved in 15.3kg vinylbenzene, and 176g graphite (UF99.5, purchased from Kropfm ü hl AG) is suspended in said mixture.
At 50l, have in the airtight stirring tank of the pressurized of paddle stirrer (blade stirrer), 20l softening water, as initial charge, is then stirred and adds 2.87kg freshly prepared Mg mentioned above under 150rpm
2p
2o
7suspension.This stirring tank has paddle stirrer, and this paddle stirrer constant agitation rotating speed with 150rpm in whole experimentation operates.For the size of agitator used and still, this is corresponding to the Mean Input Power of 0.143W/kg.
In 1.2 hours, this suspension is heated to 80 ℃, and then in 4.5 hours, is heated to 134 ℃.In temperature, reach 80 ℃ after 140 minutes, added the E30 emulsifier solution of 63.2g2% concentration (by the C of the E30-40 purchased from Leuna Tenside GmbH, 40 % by weight
12-C
17the mixture preparation of-alkyl sodium sulfonate in water).After 30 minutes, 1.17kgPentan S (Haltermann/Exxon) is metered in said mixture.Finally, under the outlet temperature of 134 ℃, complete polymerization.
The expandable polystyrene bead of gained comes separated by decant, and be dried to remove interior moisture, then with the mixture coating of glyceryl monostearate, Tristearoylglycerol and precipitated silica.The dicumyl peroxide content of EPS bead is 0.2 % by weight, and its sieve material distributes as follows:
Comparative example 2 (with US6,130,265 embodiment 3 is similar)
Repeat comparative example 1, difference is 636g graphite (4 % by weight) to be added in organic phase.
Inventive embodiments 1:
Step a)
Prepare styrene polymer bead
Prepare by the following method organic phase: by 2.80kg comparative example 2 EPS, 756g hexabromocyclododecane (Chemtura), the 9.00g2-ethyl peroxy caproic acid tert-butyl ester (Trigonox21S, AkzoNobel), 182g dicumyl peroxide (Perkadox BC-FF, AkzoNobel), 18.0g peroxidation two (hexadecyl) two carbonic ether (Perkadox24-FL, AkzoNobel) and 420g white oil (Winog70) be dissolved in 14.0kg vinylbenzene, and 2.10kg graphite (UF99.5, Kropfm ü hl AG) is suspended in this mixture.
At 50l, have in the airtight stirring tank of the pressurized of paddle stirrer, 15l softening water, as initial charge, is then stirred and adds 5.22kg freshly prepared Mg mentioned above under 240rpm
2p
2o
7suspension.This stirring tank has paddle stirrer, and this paddle stirrer constant agitation rotating speed with 240rpm in whole experimentation operates.For the size of agitator used and still, this is corresponding to the Mean Input Power of 0.579W/kg.
In 1.5 hours, this suspension is heated to 95 ℃, and then in 4.2 hours, is heated to 127 ℃.In temperature, reached 80 ℃ after 100 minutes, by the E30 emulsifier solution of 240g2% concentration (by the E30-40 purchased from Leuna Tenside GmbH, C
12-C
17the mixture preparation of-alkyl sodium sulfonate) be metered in said mixture.Finally, under the outlet temperature of 127 ℃, complete polymerization.
The interior moisture content of styrene polymer bead is 5.23%, and its mean diameter is 0.8mm.
Step b)
The styrene polymer bead of gained is filtered by suction funnel (suction filter funnel, aperture 40 μ m), and be dried to remove surface water.
Steps d) main polyreaction
Using the E30 emulsifier solution of 600g softening water, 200g MPP suspension and 18.8g1% concentration (being prepared by the E30-40 from Leuna Tenside GmbH) as initial charge, be fed in 2l stirring tank, then add 250g styrene polymer bead.In 1 minute, under agitation, the 3.50g2-ethyl peroxy caproic acid tert-butyl ester (Trigonox21S, AkzoNobel) is dropwise added in this suspension.Sealing stirring tank, and within the time of 10 minutes, in this stirring tank, add 50g vinylbenzene.Once temperature has reached 90 ℃, in 95 minutes, add other 533g vinylbenzene.Then this reaction mixture is heated to 130 ℃.Since the temperature of 120 ℃, within the time of 40 minutes, add 67g Pentan S (Haltermann/Exxon).At the temperature of 130 ℃, under agitation, continue polymerization 2 hours, to realize monomer, transform completely.
The polystyrene bead that comprises whipping agent of gained comes separated by decant, and be dried to remove interior moisture, then with the coating composition coating of glyceryl monostearate, Tristearoylglycerol and precipitated silica.The bead size-grade distribution of gained EPS bead is as follows:
Inventive embodiments 2a:
Repeat inventive embodiments 1, difference is styrene polymer bead by the sieve purchased from Fritsch (Analysette18), to sieve subsequently.Main polyreaction is subsequently used the sieve material of 0.4mm to 1.25mm.
Inventive embodiments 2b
Repeat inventive embodiments 2a, difference is in main polyreaction, before the heating phase starts, will be dissolved in the cinnamic 2.92g dicumyl peroxide of 5g and be added in cold reactor in 2 minutes.Dry polymer obtains white that following sieve material distributes and the polymkeric substance of graphitiferous not:
Inventive embodiments 3
Repeat inventive embodiments 1, difference is styrene polymer bead by the sieve purchased from Fritsch (Analysette18), to sieve (step c) subsequently.Main polyreaction is subsequently used the sieve material of 0.5mm to 1.25mm.
Inventive embodiments 4
Repeat inventive embodiments 2, difference is to use 420g1, and 2-cyclohexane dicarboxylic acid diisononyl esters (Hexamoll Dinch, BASF SE) substitutes white oil.The interior water content of styrene polymer bead is 4.76%.Main polyreaction is subsequently used the sieve material of 0.4mm to 1.25mm.
Inventive embodiments 5
Repeat inventive embodiments 2, difference is to use the alkyl sulfonic ester (ASE) (Mesamoll2, Lanxess AG) of 420g phenol to substitute white oil.The interior water content of styrene polymer bead is 3.16%.Main polyreaction is subsequently used the sieve material of 0.4mm to 1.25mm.
Inventive embodiments 6
Repeat inventive embodiments 2, difference is to use 1.06kg brominated styrene-butadiene block copolymer (Br-SBS) to substitute HBCD.The interior water content of styrene polymer bead is 2.56%.Main polyreaction is subsequently used the sieve material of 0.4mm to 1.25mm.
Inventive embodiments 7:
Step a)
The preparation of styrene polymer bead
Prepare by the following method organic phase: by 2.80kg comparative example 2 EPS, 756g hexabromocyclododecane (Chemtura), the 9.00g2-ethyl peroxy caproic acid tert-butyl ester (Trigonox21S, AkzoNobel), 350g dicumyl peroxide (Perkadox BC-FF, AkzoNobel), 18.0g peroxidation two (hexadecyl) two carbonic ether (Perkadox24-FL, AkzoNobel) and 420g white oil (Winog70) be dissolved in 14.0kg vinylbenzene, and 2.10kg graphite (UF99.5, Kropfm ü hl AG) is suspended in this mixture.
At 50l, have in the airtight stirring tank of the pressurized of paddle stirrer, 15l softening water, as initial charge, is then stirred and adds 5.22kg freshly prepared Mg mentioned above under 240rpm
2p
2o
7suspension.This stirring tank has paddle stirrer, and this paddle stirrer constant agitation rotating speed with 240rpm in whole experimentation operates.For the size of agitator used and still, this is corresponding to the Mean Input Power of 0.579W/kg.
In 1.5 hours, this suspension is heated to 95 ℃, and then in 4.2 hours, is heated to 125 ℃.In temperature, reached 80 ℃ after 100 minutes, by the E30 emulsifier solution of 240g2% concentration (by the E30-40 purchased from Leuna Tenside GmbH, C
12-C
17the mixture preparation of-alkyl sodium sulfonate) be metered in said mixture.Finally, under the outlet temperature of 125 ℃, complete polymerization.
Step b)
The styrene polymer bead of gained comes separated by decant, and is dried to remove surface water, and sieves.
Step c)
Main polyreaction is subsequently used the sieve material of 0.4mm to 1.25mm.
Steps d) main polyreaction
At 2.4l stirring tank (intersection paddle stirrer, 360rpm), using the E30 emulsifier solution of 596g softening water, 196g MPP suspension and 18.5g1% concentration (being prepared by the E30-40 from Leuna Tenside GmbH) as initial charge, then add 245g through the styrene polymer bead of screening.In the still of sealing, introduce nitrogen (0.5 bar), and at room temperature in 6 minutes, 30g vinylbenzene is added in still.In 61 minutes, reactor is heated to 125 ℃, and in 105 minutes, adds other 557g vinylbenzene.Then within the time of 40 minutes, add 65g Pentan S (Haltermann/Exxon).At the temperature of 130 ℃, under agitation, continue repolymerization 2 hours, be achieved conversion of monomer completely, and then mixture be cooled to room temperature.
The polystyrene bead that comprises whipping agent of gained comes separated by decant, and be dried to remove interior moisture, then with the coating composition coating of glyceryl monostearate, Tristearoylglycerol and precipitated silica.The bead size-grade distribution of gained EPS bead is as follows.
In experimentation, extract sample.Remove the polymer beads obtaining after water and measure residual monomer by HPLC, and by GPC determining molecular weight.Residual monomer content when polyreaction finishes is 0.22 % by weight.Weight-average molecular weight: M
w247900, number-average molecular weight: M
n77610, and polydispersity: D=3.19.
Inventive embodiments 8:
Step a)
Prepare styrene polymer bead
Prepare by the following method organic phase: by 52.3kg comparative example 2 EPS, 18.8kg hexabromocyclododecane (Chemtura), the 224g2-ethyl peroxy caproic acid tert-butyl ester (Trigonox21S, AkzoNobel), 8.71kg dicumyl peroxide (Perkadox BC-FF, AkzoNobel), 437g peroxidation two (hexadecyl) two carbonic ether (Perkadox24-FL, AkzoNobel) and 10.4kg white oil (Winog70) be dissolved in 328.2kg vinylbenzene, and 52.3kg graphite (UF99.5, Kropfm ü hl AG) is suspended in this mixture.
At 1m
3have in the pilot scale still of intersection paddle stirrer, as initial charge, under 240rpm stirs, in described initial charge, add 171.1kg to be similar to freshly prepared Mg mentioned above 378.0kg softening water
2p
2o
7suspension and 828g bitter salt (Epsom salt), and the organic phase from batch still is metered in described mixture.Then agitator speed is made as to 68rpm (corresponding to the Mean Input Power of 0.29W/kg).
In 1.5 hours, this suspension is heated to 95 ℃, and then in 4.2 hours, is heated to 125 ℃.In temperature, reached 80 ℃ after 89 minutes, by the E30 emulsifier solution of 4.00kg2% concentration (by the E30-40 purchased from Leuna Tenside GmbH, C
12-C
17the mixture preparation of-alkyl sodium sulfonate) be metered in said mixture.After adding emulsifying agent, agitator speed is down to 42rpm (corresponding to the Mean Input Power of 0.070W/kg).Finally, under the outlet temperature of 125 ℃, complete polymerization.
Step b)
The prepolymer of gained is by (Conturbex H320) screen centrifuge (0.2mm sieve aperture) that 200ppm E30 emulsifying agent is housed purchased from Siebtechnik, provide antistatic property to carry out separation by means of conveying screw rod, and dry to remove surface water by means of pneumatic dryer (medial temperature: 70 ℃).The interior moisture content of the styrene polymer bead of gained is 7.56%, and its dicumyl peroxide content is 1.44 % by weight.
Step c) screening
Pre-screening styrene polymer bead: the sieve material that sieves out 0.4mm to 1.25mm.
Steps d) main polyreaction
2.4l stirring tank (intersect paddle stirrer, 360rpm) in, using the E30 emulsifier solution of 534g softening water, 178g MPP suspension and 17.2g1% concentration (being prepared by the E30-40 from Leuna Tenside GmbH) as initial charge.Then pack 236.9g into through the styrene polymer bead of screening.Nitrogen (0.5 bar) is introduced in the still of sealing, and at room temperature in 6 minutes, in still, adds 31.4g vinylbenzene.In 61 minutes, the inclusion of reactor is heated to 125 ℃, and then in 105 minutes, adds other 522.6g vinylbenzene.Then within the time of 40 minutes, add 63g Pentan S (Haltermann/Exxon).Make this mixture at the temperature of 125 ℃, keep other 95 minutes, and in 30 minutes, the inclusion of agitator is heated to 130 ℃, and continue other 30 minutes of polymerization at 130 ℃.
The polystyrene bead that comprises whipping agent of gained comes separated by decant, and be dried to remove interior moisture, then with the coating composition coating of glyceryl monostearate, Tristearoylglycerol and precipitated silica.The bead size-grade distribution of the EPS bead of gained is summarized in following table 3.
In experimentation, extract sample.Remove the polymer beads obtaining after water and measure residual monomer by HPLC, and by GPC determining molecular weight.Residual monomer content when polyreaction finishes is 0.18 % by weight.Weight-average molecular weight: M
w251610, number-average molecular weight: M
n84841, and polydispersity: D=2.97.
Inventive embodiments 9:
Step a) is prepared styrene polymer bead
Prepare by the following method organic phase: by the styrene polymer bead of 420g inventive embodiments 8,219g hexabromocyclododecane (Chemtura), the 1.80g2-ethyl peroxy caproic acid tert-butyl ester (Trigonox21S, AkzoNobel), 108g dicumyl peroxide (Perkadox BC-FF, AkzoNobel) and 3.5g peroxidation two (hexadecyl) two carbonic ether (Perkadox24-FL, AkzoNobel) be dissolved in 2.8kg vinylbenzene, and 588kg graphite (UF99.5, Kropfm ü hl AG) is suspended in this mixture.
Organic phase is introduced into 10l stirring tank (paddle stirrer, 300rpm, corresponding to the Mean Input Power of 0.584W/kg) in the 3.04l softening water that contains 1.60kg MPP suspension and 7.90g bitter salt (Epsom salt) (Kali und Salz) in.In 1.5 hours, this suspension is heated to 95 ℃, and then in 4.2 hours, is heated to 125 ℃.In temperature, reached 80 ℃ after 85 minutes, the E30 emulsifier solution of 37g2% concentration (Leuna Tenside GmbH) has been metered in said mixture.Finally, under the outlet temperature of 125 ℃, complete polymerization.
Step b)
The styrene polymer bead of gained comes separated by decant, and is dried to remove surface water.
Step c) screening
Pre-screening styrene polymer bead: the sieve material that sieves out 0.45mm to 1.00mm.
Steps d) main polyreaction
2.4l stirring tank (intersect paddle stirrer, 360rpm) in, using the E30 emulsifier solution of 534g softening water, 178g MPP suspension and 17.2g1% concentration (being prepared by the E30-40 from Leuna Tenside GmbH) as initial charge.Then add 181g through the styrene polymer bead of screening.Nitrogen (0.5 bar) is introduced in the still of sealing, and at room temperature in 6 minutes, in still, adds 27.3g vinylbenzene.The inclusion of reactor is heated to the temperature of 125 ℃ in 61 minutes, and then in 105 minutes, adds other 577g vinylbenzene.Reaching the temperature of 125 ℃ after 150 minutes, within the time of 40 minutes, add 63g Pentan S (Haltermann/Exxon).At the temperature of 130 ℃, finish polyreaction.
The polystyrene bead that comprises whipping agent of gained comes separated by decant, and be dried to remove interior moisture, then with the coating composition coating of glyceryl monostearate, Tristearoylglycerol and precipitated silica.The bead size-grade distribution of gained EPS bead is summarized in table 3.
In experimentation, extract sample.Remove the polymer beads obtaining after water and measure residual monomer by HPLC, and by GPC determining molecular weight.Residual monomer content when polyreaction finishes is 0.31 % by weight.Weight-average molecular weight: M
w202310, number-average molecular weight: M
n70665, and polydispersity: D=2.86.
Inventive embodiments 10
Step a) is prepared styrene polymer bead
Prepare by the following method organic phase: by 2.1kg EPS (as prepared in comparative example 2), 892g Br-SBC, the 9.00g2-ethyl peroxy caproic acid tert-butyl ester (Trigonox21S, AkzoNobel), 365g dicumyl peroxide (Perkadox BC-FF, AkzoNobel), 18.0g peroxidation two (hexadecyl) two carbonic ether (Perkadox24-FL, AkzoNobel) and 420g white oil (Winog70) be dissolved in 14.0kg vinylbenzene, and 2.17kg graphite (UF99.5, Kropfm ü hl AG) is suspended in this mixture.
Organic phase is introduced in the 15l softening water that contains 5.22kg MPP suspension in 50l stirring tank (paddle stirrer, 240rpm, corresponding to the Mean Input Power of 0.579W/kg).In 1.5 hours, this suspension is heated to 95 ℃, and then in 4.20 hours, is heated to 125 ℃.In temperature, reached after 80 ℃ 100 minutes (+/-5 minutes), the E30 emulsifier solution of 240g2% concentration (prepared by the E30-40 by Leuna Tenside GmbH) has been metered in said mixture.Finally, under the outlet temperature of 125 ℃, complete polymerization.
Step b)
The styrene polymer bead of gained comes separated by decant, and is dried to remove surface water by air stream drying method.The limiting viscosity IV of styrene polymer bead is 74.6, corresponding to the weight-average molecular weight of about 200000g/mol.Residual moisture content is 1.48 % by weight, and residual monomer content is 0.02 % by weight.EPS bead has following bead and distributes:
Step c) screening
Pre-screening styrene polymer bead: sieve out the sieve material of 0.4mm to 1.12mm, then for main polyreaction.
Steps d) main polyreaction
At 10l stirring tank (intersection paddle stirrer, 170rpm), using the 3.24kg softening water of the E30 emulsifier solution that contains 1.08kg MPP suspension and 51g2% concentration (being prepared by the E30-40 from Leuna Tenside GmbH) as initial charge.Then add 1.44kg through the styrene polymer bead of screening.Then nitrogen (0.5 bar) is introduced in the still of sealing, and at room temperature in 10 minutes, adds 320ml vinylbenzene.In 137 minutes, the inclusion of reactor is heated to 125 ℃, and then in 87 minutes, adds other 3.39l vinylbenzene.In temperature, reach 125 ℃ after 27 minutes, within the time of 60 minutes, added 307g Pentan S (Haltermann/Exxon).In temperature, reached 125 ℃ after 110 minutes, in 1 hour, be warming up to 135 ℃, and at this temperature, complete polymerization (residual monomer content <1000ppm).
The polystyrene bead that comprises whipping agent of gained comes separated by decant, and be dried to remove interior moisture, then with the coating composition coating of glyceryl monostearate, Tristearoylglycerol and precipitated silica.Weight-average molecular weight is M
w: 338200g/mol.The EPS bead of gained has following bead size-grade distribution.
The sieve material of table 1. styrene polymer bead distributes
The sieve material of table 2:EPS bead distributes
| Particle diameter | Inventive embodiments 3 | Inventive embodiments 4 | Inventive embodiments 5 | Inventive embodiments 6 |
| >2.5mm | 0.01％ | 0.06％ | 0.07％ | 4.07％ |
| 1.4–2.5mm | 21.03％ | 14.28％ | 9.92％ | 24.06％ |
| 0.8–1.4mm | 78.37％ | 71.67％ | 77.13％ | 61.56％ |
| 0.4–0.8mm | 0.39％ | 12.45％ | 12.48％ | 10.05％ |
| 0–0.4mm | 0.20％ | 1.54％ | 0.4％ | 0.26％ |
The sieve material of table 3:EPS bead distributes
| Particle diameter | Inventive embodiments 7 | Inventive embodiments 8 | Inventive embodiments 9 |
| >2.5mm | ? | ? | 0.26％ |
| 2.0–2.5mm | 0.85％ | ? | 0.38％ |
| 1.6–2.0mm | 0.95％ | 0.29％ | 2.60％ |
| 1.4–1.6mm | 1.4％ | 6.49％ | 5.62％ |
| 1.25–1.4mm | 15.96％ | 16.84％ | 10.52％ |
| 1.0–1.25mm | 40.33％ | 38.12％ | 36.11％ |
| 0.8–1mm | 33.72％ | 24.93％ | 30.82％ |
| 0.63–0.8mm | 5.44％ | 13.08％ | 10.82％ |
| 0.5–0.63mm | 0.8％ | 0.85％ | 1.79％ |
| 0.4–0.5mm | 0.14％ | 0.13％ | 0.62％ |
| 0.2–0.4mm | 0.01％ | 0.12％ | 0.28％ |
| >0.2mm | ? | 0.09％ | 0.16％ |
| D'(calculates) | ? | 1.15mm | 1.146mm |
| β (calculating) | ? | 10.72 | 10.88 |
Claims (10)
1. a styrene polymer bead material, one or more high temperature superoxide that wherein styrene polymer bead comprises 0.5 to 5 % by weight, the transformation period that wherein said high temperature superoxide is measured within the scope of 110 to 160 ℃ in isopropyl benzene is 1 hour.
2. the styrene polymer bead material of claim 1, it comprises 0.5 to 5 % by weight as the dicumyl peroxide of high temperature superoxide.
3. claim 1 or 2 styrene polymer bead material, one or more particulate additives that it comprises 5 to 50 % by weight.
4. the styrene polymer bead material of claim 3, it comprises 5 to 50 % by weight as the carbon granule of particulate additives.
5. the styrene polymer bead material of any one in claim 1 to 4, the graphite granule of its median size that comprises 5 to 50 % by weight within the scope of 1 to 50 μ m.
6. the styrene polymer bead material of any one in claim 1 to 5, the graphite granule of its median size that comprises 5 to 30 % by weight within the scope of 1 to 50 μ m and 5 to 30 % by weight are as the organbromine compound of fire retardant.
7. the styrene polymer bead material of any one in claim 1 to 6, it is containing whipping agent.
8. a method of preparing the styrene polymer bead material of claim 1, it is included under the maximum temperature of 130 ℃ polymerizing styrene monomer in the waterborne suspension under the existence of the high temperature superoxide of 0.5 to 5 % by weight and the low temperature superoxide of 0.1 to 3 % by weight, and wherein suspension polymerization is less than the time of 1.5h in the temperature range of 120-130 ℃.
In claim 1 to 7 the styrene polymer bead material of any one as the purposes of the seed in suspension polymerization.
10. a method of preparing expandable styrene-polymer, it comprises that right to use requires styrene polymer bead material of any one in 1 to 7 as the seed in styrene monomer suspension polymerization, and during polyreaction or add afterwards whipping agent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11194867 | 2011-12-21 | ||
| EP11194867.5 | 2011-12-21 | ||
| PCT/EP2012/075722 WO2013092466A1 (en) | 2011-12-21 | 2012-12-17 | High-temperature peroxide-containing styrene polymer beads for seed polymerization |
Publications (1)
| Publication Number | Publication Date |
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| CN104011120A true CN104011120A (en) | 2014-08-27 |
Family
ID=47429806
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280063951.2A Pending CN104011120A (en) | 2011-12-21 | 2012-12-17 | High-temperature peroxide-containing styrene polymer beads for seed polymerization |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20150322182A1 (en) |
| EP (1) | EP2794739A1 (en) |
| KR (1) | KR20140095584A (en) |
| CN (1) | CN104011120A (en) |
| BR (1) | BR112014015258A8 (en) |
| MX (1) | MX2014007311A (en) |
| WO (1) | WO2013092466A1 (en) |
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| KR102209565B1 (en) | 2013-11-14 | 2021-02-01 | 가부시키가이샤 가네카 | Extruded styrenic resin foam and method for manufacturing same |
| CN105873961B (en) | 2013-12-30 | 2018-10-19 | 艾凡瑞斯公司 | The method for preparing solid granular vinylaromatic polymer composition |
| KR101713656B1 (en) * | 2015-12-08 | 2017-03-22 | 금호석유화학 주식회사 | Method for producing expandable polystyrene large beads having excellent thermal insulation performance |
| HUE051339T2 (en) * | 2016-03-18 | 2021-03-01 | Nouryon Chemicals Int Bv | Storage stable aqueous organic peroxide emulsions |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1269814A (en) * | 1997-09-29 | 2000-10-11 | 巴斯福股份公司 | Method for producing expandable styrene polymers |
| CN1352658A (en) * | 1999-04-09 | 2002-06-05 | 聚合物系统有限公司 | Preparation of polymer particles |
| WO2010066331A1 (en) * | 2008-12-12 | 2010-06-17 | Jackon Gmbh | Process for the preparation of an expandable polymer composition in the form of beads |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6213442A (en) | 1985-07-12 | 1987-01-22 | Mitsubishi Yuka Badische Co Ltd | Production of carbon-containing expandable styrene resin particle |
| DE4220225A1 (en) | 1992-06-20 | 1993-12-23 | Basf Ag | Process for the production of pearl-shaped expandable styrene polymers |
| ES2151270T3 (en) * | 1997-05-14 | 2000-12-16 | Basf Ag | PROCEDURE FOR OBTAINING EXPANDABLE STYRENE POLYMERS CONTAINING GRAPHITE PARTICLES. |
| DE19749570A1 (en) * | 1997-11-10 | 1999-05-12 | Basf Ag | Process for the preparation of expandable styrene polymers |
| DE10150405A1 (en) | 2001-10-11 | 2003-04-17 | Basf Ag | Preparation of expanded polystyrene polymerizates in the presence of peroxides and graphite particles useful for the formation of shaped bodies, e.g. for packaging |
| US6608150B1 (en) * | 2002-10-08 | 2003-08-19 | Atofina Chemicals, Inc. | Preparation of expandable styrene polymers |
| KR100801275B1 (en) | 2006-03-31 | 2008-02-04 | 금호석유화학 주식회사 | Method for producing expandable polystyrene beads which have excellent heat insulation properties |
| JP5080226B2 (en) | 2007-12-07 | 2012-11-21 | 積水化成品工業株式会社 | Expandable resin particles, method for producing the same, and foam molded article |
| ATE549610T1 (en) | 2008-07-16 | 2012-03-15 | Siemens Ag | ARRANGEMENT WITH AN ELECTRICAL MACHINE AND METHOD FOR OPERATING AN ELECTRICAL MACHINE |
-
2012
- 2012-12-17 EP EP12806025.8A patent/EP2794739A1/en not_active Withdrawn
- 2012-12-17 CN CN201280063951.2A patent/CN104011120A/en active Pending
- 2012-12-17 KR KR1020147020272A patent/KR20140095584A/en not_active Application Discontinuation
- 2012-12-17 WO PCT/EP2012/075722 patent/WO2013092466A1/en active Application Filing
- 2012-12-17 US US14/367,258 patent/US20150322182A1/en not_active Abandoned
- 2012-12-17 MX MX2014007311A patent/MX2014007311A/en not_active Application Discontinuation
- 2012-12-17 BR BR112014015258A patent/BR112014015258A8/en not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1269814A (en) * | 1997-09-29 | 2000-10-11 | 巴斯福股份公司 | Method for producing expandable styrene polymers |
| CN1352658A (en) * | 1999-04-09 | 2002-06-05 | 聚合物系统有限公司 | Preparation of polymer particles |
| WO2010066331A1 (en) * | 2008-12-12 | 2010-06-17 | Jackon Gmbh | Process for the preparation of an expandable polymer composition in the form of beads |
Also Published As
| Publication number | Publication date |
|---|---|
| US20150322182A1 (en) | 2015-11-12 |
| BR112014015258A2 (en) | 2017-06-13 |
| EP2794739A1 (en) | 2014-10-29 |
| BR112014015258A8 (en) | 2017-07-04 |
| WO2013092466A1 (en) | 2013-06-27 |
| MX2014007311A (en) | 2014-07-30 |
| KR20140095584A (en) | 2014-08-01 |
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Application publication date: 20140827 |